Recycling of commingled plastics by cellulosic reinforcement

In this article, a model study was conducted on the effect of combining cellulose on the properties of virgin and/or recycled commingled plastics with a simulated waste‐plastics fraction composed of high‐density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), and poly(vinyl chloride) (PVC) (PE/PP/PS/PVC = 7/1/1/1 by weight ratio). The compatibilizing effect of maleic anhydride‐grafted styrene–ethylene/butylene–styrene block copolymer (SEBS‐g‐MAH) for the cellulose‐reinforced commingled blends was also investigated. Commingled blends were prepared in a table kneader internal mixer. Mechanical properties were measured by using a universal testing machine. Thermal stability was measured by a thermogravimetric analyzer. It was found that the addition of more than 12.5% cellulose into the commingled blends was effective to enhance the mechanical properties of the virgin and recycled blends. The thermal stability as well as the mechanical properties of the commingled blends were much improved by the reactive blending of cellulose with the commingled blends by peroxide and maleic anhydride. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1531–1538, 1999     

Recycling of EPDM waste. II. Replacement of virgin rubber by ground EPDM vulcanizate in EPDM/PP thermoplastic elastomeric composition

Virgin ethylene propylene diene monomer (EPDM) rubber in a thermoplastic elastomeric blend of polypropylene (PP) and EPDM rubber was substituted by ground EPDM vulcanizate of known composition, after which the mechanical properties of the raw EPDM/waste EPDM/PP blends were determined. The ratio of the rubber content in the waste EPDM (r‐W‐EPDM) to the raw EPDM (R‐EPDM) in the blends was varied from 0 : 100 to 45 : 55. Attempts to replace higher amounts (>45%) of R‐EPDM by W‐EPDM failed because of processing difficulty. Although a drop in mechanical properties of the blends was observed at lower loadings of W‐EPDM, the properties showed improvement at intermediate W‐EPDM loadings. The R‐EPDM/W–EPDM/PP blends were found to be reprocessable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3304–3312, 2001     

Application of phase dispersion–crosslinking synergism on recycling commingled plastic wastes

A tetra‐component blend, consisting of low‐density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene (PP), and polystyrene (PS), was studied as a model system of commingled plastic wastes (LDPE/PVC/PP/PS, mass ratio: 70/10/10/10). Effects of chlorinated polyethylene (CPE), ethylene–propylene–diene monomer (EPDM), styrene–butadiene–styrene (SBS), and their mixture (CPE/EPDM/SBS, mass ratio: 2/2/2) on the mechanical properties and morphology of the system were investigated. With addition of several elastomers and their mixture, the tensile strength of the blends decreased slightly, although both the elongation at break and the impact strength increased. Among these elastomers, EPDM exhibited the most significant impact modification effect for the tetra‐component blends. SBS and the mixture have a good phase‐dispersion effect for the tetra‐component blend. By adding a crosslinking agent [dicumyl peroxide (DCP)], the mechanical properties of the tetra‐component blends also increased. When either SBS or the mixture was added to the blend together with DCP, the probability that the crosslinking agent (DCP) would be at the interface improved because of the phase‐dispersion effect of SBS. Therefore, more co‐crosslinked products will form between LDPE and other components. Accordingly, remarkable improvement of the interfacial adhesion and hence the mechanical properties of the tetra‐component blends occurred. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2947–2952, 2001     

聚烯烃改性PET的研究

通过PET与PP、HDPE、EPDM挤出共混，注射模塑制得试样。经DTA、SEM和力学性能测试，表征了共混体系的热行为、结构形态和力学性能。结果表明，在PET/PP(EPDM、HDPE)共混体系中，加入少量的PP-g-MI(EPDM-g-MAH、PE-g-MI)，可较好地改善PEt与PP(EPDM、HDPE)之间的相容性，使分散相在PET基体连续相中分散均匀，分散相尺寸减小，增加了两相间界面的粘结力；同时对PET的结晶有较强的促进作用，使其冷结晶温度降低，改善了PET的加工性能；并且能大幅度提高共混物的冲击强度。     

PP／PE复合基材及其增韧研究

研究了PP/PE共混复合基材的力学性能和形态结构与组成配比的关系.结果表明,PP/HDPE/EPDM和PP/LLDPE共混体系可以制成具有高抗冲击性能的复合基材,且其他力学性能均衡,加工性能良好。弹性体SRS对复合基材的力学性能及形态有较大影响.实验结果表明,LLDPE具有分割、插入、细化PP球晶的作用,并与PP有较好的相容性;EPDM对PP/HDPE共混体系具有良好的增容效果。     

Analysis of polyolefin blends by crystallization analysis fractionation

Crystallization analysis fractionation (CRYSTAF) is a new technique for the analysis of the composition of polyolefin blends. CRYSTAF fractionates blend components of different crystallizability by slow cooling of a polymer solution. During the crystallization step the concentration of the polymer solution is monitored as a function of temperature. Different from DSC, blends of HDPE, LDPE and PP are separated into the components and quantitative information can be obtained directly from the crystallization curves. Even very low amounts of one component in PE/PP and HDPE/LDPE blends can be quantified with good accuracy. The applicability of the technique for the analysis of Ziegler‐Natta, and metallocene‐catalyzed polyolefins is demonstrated and the analysis of waste plastics fractions is discussed.     

Product design with glass fiber reinforced polymer blends,with potential applications in recycling

This paper addresses the issue of compositional variation in multiphase, multi-component polymer mixtures equivalent to those found in commingled waste streams, such as those obtained from reclamation/recycling operations of post-consumer containers. By using virgin resins, the effects of variations in the composition of matrices containing high density polyethylene (HDPE) as the major phase on the properties of composites containing varying amounts of glass fiber and different adhesion promoters are studied. The results obtained on injection molded thin-section parts indicate that it is possible, through the addition of glass fibers and in the presence of suitable adhesion promoters, to obtain enhanced and reproducible properties with relatively little dependence on matrix composition. Preliminary structural and flow analyses were performed with commercial software on different types of plastic parts that could be eventually molded from actual mixed waste plastics suitably modified through glass reinforcement. Experimentally generated rheological and mechanical property data on HDPE based blends containing 20 wt% glass fibers and different adhesion promoters were used for the simulation. Issues concerned with injection molding and product performance of glass-fiber reinforced blends are discussed.     

Thermoplastic composites from maleic anhydride modified post-consumer plastics

In attempts to identify potential applications for refined commingled postconsumer plastics, a feedstock containing about 80% polyethylene (PE) and lesser amounts of poly(ethylene terephthalate) (PET), polystyrene (PS), polypropylene (PP), and poly(vinyl chloride) (PVC) was modified through functionalization with maleic anhydride in a co-rotating intermeshing twin-screw extruder. The modified and unmodified blends were compounded with various fillers and reinforcements such as glass fibers, mica flakes, talc, and calcium carbonate. Injection molded composites based on the modified matrix had, in general, superior mechanical and thermal properties. These findings are discussed in view of the improved adhesion resulting from reactions and/or enhanced polar interactions at phase boundaries. Several compounds prepared in this work had overall property data comparable to, or approaching those, of equivalent commercial HDPE molding compounds that are commonly used in “durable” applications.     

再生聚合物异性混容技术研究

综述了不同极性聚合物材料共混界面的相容性、改善相容性的方法以及增容技术的应用,重点介绍了利用第３组分增容双组分（聚丙烯／聚氯乙烯）和多组分混杂废旧异性塑料共混物的混容技术。对通过粉碎技术、注挤法成型、挤出成型、模压成型、注射成型等５种加工方法获得高附加值制品的加工工艺及相关设备的研究现状做了介绍。此外,对如何进一步开展不分类废旧塑料的再生利用提出了一些建议。     

用于交通信号标识制品的聚丙烯合金的研制

以PP为基体，加入EPDM和HDPE，采用动态硫化技术，制得了可用于交通信号标识制品的PP合金，并分别对材料的力学性能、热性能和加工流动性进行了评估。实验表明，PP／HDPE／EPDM能很好地改善PP的低温脆性，是制造交通信号标识制品的理想材料。     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Mechanical properties-structure relationships of crosslinked blends based on LDPE/HDPE waste

Low-density polyethylene (LDPE) waste was blended with high-density polyethylene (HDPE) waste of different degrees of degradation. Structural, mechanical and rheological properties of these blends were investigated. It was found that 2 wt.-% of dicumyl peroxide improves simultaneously the tensile strength and elongation at break without serious decrease of the melt elasticity of separate PE wastes and their binary blends in comparison with unmodified PE. It was shown by DSC analyses that modification of the blends leads to better compatibility between LDPE and HDPE.     

粉状聚丙烯增韧增强研究

采用机械共混方法对粉状聚丙烯（PP）进行了增韧增强研究，探讨了增韧剂、增强剂和有少量自制的固相甲基丙烯酸（MAA）接枝粉状聚丙烯（PP-g-MAA)作增容剂存在下对粉状PP共混体系力学性能的影响，用热重分析法考察了改性粉状PP的热性能。结果表明，（乙烯／丙烯／二烯）共聚物（EPDM）／高密度聚乙烯（HDPE）为复合增韧剂，具有协同作用，可显著提高共混物的冲击强度：PP-g-MAA能明显改善PP／玻纤两相的界面结合力；PP／EPDM／HDPE玻璃纤维共混体系可以获得理想的增韧增强效果。     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

Mechanical Properties and Morphology of Ternary PP/EPDM/PE Blends

The ternary blends of high‐density polyethylene (PE), EPDM terpolymer and polypropylene (PP) have been used as a model low interfacial tension system to study encapsulation dynamics in ternary blends and their relation to the blends' mechanical properties. It was found that the modulus, tensile strength and impact resistance can be improved by PE addition if the PE is localized within the EPDM phase. A range of blend morphology was found depending on the PE viscosity and polymer incorporation sequence in the twin‐screw extruder. In the most favorable sequence, PE and EPDM were mixed together prior to their dispersion in the PP matrix. This practice resulted in a 50% increase in impact resistance when compared to mixing the three components in a single‐step.     

Compatibilization of PP/PE blends and scraps with Royalene: Mechanical properties,SAXS, and WAXS

PP/PE 93/7 model virgin blends and recycled scraps were compatibilized with Royalene (EPDM/PE 65/35 blend) and mechanically tested. No differences in impact and tensile properties between them were found. However, the tensile-impact strength increased almost twice with 10%-compatibilized sample in comparison with uncompatibilized ones. The yield stress of blends containing 10% Royalene decreased to 75–80% of the original value. This effect is in agreement with microhardness measurements; the increase in the compatibilizer content causes softening of the blend. The elongation at break and elongation at yield do not depend on the compatibilizer concentration. The compatibilizer does not influence the degree of crystallinity (WAXS data) of the blends either. Vickers microhardness is in good agreement with Tabor's relationship. The differences between long periods of HDPE in Royalene and LDPE in PP/PE blends (SAXS) proved PE/EPDM interaction. The interaction plays a key role in the toughening of PP/PE blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

The Effect of Vibration on Mechanical Properties of Blends of EPDM/PP in a Tri-screw Dynamic Mixing Extruder

The effects of vibration force field on mechanical properties of blends of EPDM/PP during process of plastics in tri-screw dynamic mixing extruders were investigated experimentally. It was found that vibration force field enhanced mechanical properties of blends of EPDM/PP, and the amplitude of enhancement varied as EPDM content varying. The yangs modulus, the impact strength and the tensile strength were improved the maximum 17, 28, and 17.3%, respectively under dynamic conditions than that under steady conditions. Mechanical properties of blends of EPDM/PP represented a tendency of a rising followed by a fall with the increase of vibration frequency and amplitude.     

Miscibility of blends of ethylene‐propylene‐diene terpolymer and polypropylene

The miscibility of polymers is not only an important basis for selecting a proper blending method, but it is also one of the key factors in determining the morphology and properties of the blends. The miscibility between ethylene‐propylene‐diene terpolymer (EPDM) and polypropylene (PP) was explored by means of dynamic mechanical thermal analysis, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results showed that a decrease in the PP content and an increase of the crosslinking density of EPDM in the EPDM/PP blends caused the glass‐transition temperature peaks of EPDM to shift from a lower temperature to higher one, yet there was almost no variance in the glass‐transition temperature peaks of PP and the degree of crystallinity of PP decreased. It was observed that the blends prepared with different mixing equipment, such as a single‐screw extruder and an open mill, had different mechanical properties and blends prepared with the former had better mechanical properties than those prepared with the latter. The TEM micrographs revealed that the blends were composed of two phases: a bright, light PP phase and a dark EPDM phase. As the crosslinking degree of EPDM increased, the interface between the phases of EPDM and PP was less defined and the EPDM gradually dispersed in the PP phase became a continuous phase. The results indicated that EPDM and PP were both partially miscible. The mechanical properties of the blends had a lot to do with the blend morphology and the miscibility between the blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 315–322, 2002